A recently reported class of microporous compositions and the first framework oxide molecular sieves synthesized without silica, are the crystalline aluminophosphate compositions disclosed in U.S. Pat. No. 4,310,440 issued Jan. 12, 1982 to Wilson et al. These materials are formed from AlO.sub.2 and PO.sub.2 tetrahedra and have electrovalently neutral frameworks as in the case of silica polymorphs. Unlike the silica molecular sieve, silicalite, which is hydrophobic due to the absence of extra-structural cations, the aluminophosphate molecular sieves are moderately hydrophilic, apparently due to the difference in electronegativity between aluminum and phosphorus. Their intracrystalline pore volumes and pore diameters are comparable to those known for zeolites and silica molecular sieves.
In commonly assigned U.S. Pat. No. 4,567,029, issued on Jan. 28, 1986, a novel class of crystalline microporous metal aluminophosphate compositions are described which contain as lattice constituents in addition to AlO.sub.2 and PO.sub.2 structural units, one or more of the metals Mg, Mn, Co, and Zn in tetrahedral coordination with oxygen atoms. This patent is herein incorporated by reference. The metal aluminophosphate compositions (hereinafter .cent.MeAPO") have an essential empirical chemical composition, on an anhydrous basis, of: EQU mR: (M.sub.x Al.sub.y P.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represent the moles of "R" present per mole of (M.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 0.3, the maximum value in each case depending upon the molecular dimensions of the templating agent and the available void volume of the pore system of the particular metal aluminophosphate involved, "x", "y", and "z" represent the mole fractions of the metal "M", (i.e. magnesium, manganese, zinc and cobalt), aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the tetragonal compositional area defined by points A, B, C and D of the ternary diagram appearing as FIG. 1 in the patent. The said points A, B, C and D representing the following values for "x.omicron., "y", and "z":
______________________________________ Mole Fraction Point x y z ______________________________________ A 0.01 0.60 0.39 B 0.01 0.39 0.60 C 0.35 0.05 0.60 D 0.35 0.60 0.05 ______________________________________
When synthesized in accordance with the process disclosed in the patent, the minimum value of "m" in the formula above is 0.02. In a preferred sub-class of the metal aluminophosphates of this invention, the values of "x", "y" and "z" in the formula above are confined to those within the tetragonal compositional area defined by the points a, b, c and d of the ternary diagram appearing as FIG. 2 of the patent, the said points a, b, c, and d representing the following values for "x", "y" and "z":
______________________________________ Mole Fraction Point x y z ______________________________________ a 0.01 0.52 0.47 b 0.01 0.39 0.60 c 0.25 0.15 0.60 d 0.25 0.40 0.35 ______________________________________
The specific structures disclosed in U.S. Pat. No. 4,567,029, are the MeAPO-5, MeAPO-11, MeAPO-12, MeAPO-14, MeAPO-16, MeAPO-17, MeAPO-20, MeAPO-34, MeAPO-35, MeAPO-36, MeAPO-39, MeAPO-44 and MeAPO-47.
In commonly assigned U.S. Pat. No. 4,554,143, issued on Nov. 19, 1985, a novel class of crystalline microporous ferroaluminophosphate compositions are described which contain as lattice constituents in addition to AlO.sub.2 and PO.sub.2 structural units, ferric and/or ferrous iron in tetrahedral coordination with oxygen atoms. This patent is herein incorporated by reference. The ferroaluminophosphate compositions (hereinafter "FAPO") have an essential empirical chemical composition, on an anhydrous basis, of: EQU mR: (Fe.sub.x Al.sub.y P.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represent the moles of "R" present per mole of (Fe.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 0.3, the maximum value in each case depending upon the molecular dimensions of the templating agent and the available void volume of the pore system of the particular ferroaluminophosphate involved, "x", "y", and "z" represent the mole fractions of iron, aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the tetragonal compositional area defined by points A, B, C and D of the ternary diagram appearing as FIG. 1 of the patent. The said points A, B, C and D representing the following values for "x", "y", and "z":
______________________________________ Mole Fraction Point x y z ______________________________________ A 0.01 0.60 0.39 B 0.01 0.39 0.60 C 0.35 0.05 0.60 D 0.35 0.60 0.05 ______________________________________
When synthesized in accordance with the process disclosed in the patent, the minimum value of "m" in the formula above is 0.02. In a preferred sub-class of the ferroaluminophosphates of this invention, the values of "x", "y" and "z" in the formula above are confined to those within the tetragonal compositional area defined by the points a, b, c and d of the ternary diagram appearing as FIG. 2 of the patent, the said points a, b, c, and d representing the following values for "x", "y" and "z":
______________________________________ Mole Fraction Point x y z ______________________________________ a 0.01 0.52 0.47 b 0.01 0.39 0.60 c 0.25 0.15 0.60 d 0.25 0.40 0.35 ______________________________________
The specific structures disclosed in U.S. Pat. No. 4,554,143, are the FAPO-5, FAPO-11, FAPO-16, FAPO-17, FAPO-18, FAPO-34, and FAPO-35.